CN101323778B - Metakaolin-slag-based geopolymer for oil field well cementation and high-temperature retarder thereof - Google Patents
Metakaolin-slag-based geopolymer for oil field well cementation and high-temperature retarder thereof Download PDFInfo
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- CN101323778B CN101323778B CN2008100208593A CN200810020859A CN101323778B CN 101323778 B CN101323778 B CN 101323778B CN 2008100208593 A CN2008100208593 A CN 2008100208593A CN 200810020859 A CN200810020859 A CN 200810020859A CN 101323778 B CN101323778 B CN 101323778B
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- metakaolin
- slag
- temperature retarder
- high temperature
- sulfate
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- 239000002893 slag Substances 0.000 title claims abstract description 51
- 229920000876 geopolymer Polymers 0.000 title abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims description 31
- 239000003129 oil well Substances 0.000 claims description 21
- 230000003014 reinforcing effect Effects 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001864 baryta Inorganic materials 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- 229940045511 barium chloride Drugs 0.000 claims description 4
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 4
- -1 alkaline earth metal salt Chemical class 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 abstract 1
- 239000002585 base Substances 0.000 description 28
- 239000004568 cement Substances 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 235000011128 aluminium sulphate Nutrition 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011211 glass fiber reinforced concrete Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
Abstract
The invention discloses a metakaolin-slag-based geopolymer for well cementation of an oil field and a high-temperature retarder thereof, wherein the high-temperature retarder can effectively control the condensation rate of the metakaolin-slag-based geopolymer for well cementation of the oil field under the high-temperature condition. The invention relates to a metakaolin-slag-based high-temperature retarder for a geopolymer for well cementation of an oil field, which consists of the following raw materials in percentage by weight: A. at least contains 80 to 90 percent of one alkaline earth metal salt; B. at least contains 10 to 20 percent of inorganic sulfate.
Description
Technical field
The present invention relates to a kind of reinforcing oil well with geopolymer and high temperature retarder thereof, more specifically to a kind of reinforcing oil well metakaolin-slag base geological polymer and high temperature retarder thereof.
Background technology
Kaolin is a kind of important industrial non-metallic minerals, formal name used at school is hydrated aluminium silicate (aluminosilicate clays mineral), metakaolin is that a kind of kaolin is raw material, form in proper temperature calcining back (600～900 ℃) dehydration, has very strong pozzolanic activity, can be used as additive, be used for onsite concrete (GFRC and GRC), mortar, mortar, concrete and other cement products, also can be used as the oil well cement adulterant of a new generation; Blast-furnace slag is the byproduct of blast furnace ironmaking, is the high reactivity silicate that mainly exists with the vitreous state form, has higher chemical potential after levigate processing, now has been widely used in cement industry; Make the focus that metakaolin-slag base geological polymer has become the research of material circle and metakaolin and slag combined, this geopolymer is that a kind of novel alkali excites gelling material, has advantages such as high-strength, environmental protection, good endurance.Metakaolin-slag base geological polymer needs just to have preferable performance after the highly basic effect at present, therefore lack time of coagulation (under 80 ℃ of conditions, final set＜0.5h), be unfavorable for the high-temperature service construction, have a strong impact on it and promote the use of, particularly applying in the reinforcing oil well engineering.And the retardant that generally uses in cement industry mainly contains lignin, tartrate, organic acid, carbohydrate and derivative thereof etc., and these cement in the high alkali environment of geopolymer preparation, do not have delayed coagulation with retardant substantially.In addition since the working conditions of reinforcing oil well all underground even reach the degree of depth of several kms, subsurface temperature generally all compares high far above room temperature, existing retardant is in the hot environment of reinforcing oil well, more can not delay condensing of metakaolin-slag base geological polymer effectively, that have even play blood coagulation enhancing effect, and can influence the intensity of geopolymer.Therefore, the urgent need exploitation is a kind of to adapt to condition of different temperatures, time of coagulation and the controlled admixture of rate of setting to metakaolin-slag base geological polymer are the metakaolin-slag base geological polymer retardant, and the performances such as degree of mobilization to the metakaolin-slag base geological polymer slurry have no adverse effect, thereby widen the application of metakaolin-slag geopolymer aspect high temperature environmental areas such as reinforcing oil well.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that above-mentioned prior art exists, provide a kind of reinforcing oil well with the metakaolin-slag base geological polymer high temperature retarder, it can effectively control reinforcing oil well with the rate of setting of metakaolin-slag base geological polymer under hot conditions.
The present invention simultaneously also provides a kind of reinforcing oil well metakaolin-slag base geological polymer that uses this high temperature retarder preparation.
The present invention is achieved by the following technical solutions:
Reinforcing oil well of the present invention is made up of following raw materials by weight percent with the metakaolin-slag base geological polymer high temperature retarder:
A, contain a kind of alkaline earth salt 80%～90% at least;
B, contain a kind of inanimate matter vitriol 10%～20% at least.
With in the high temperature retarder, its further technical scheme is that the alkaline-earth metal described in the described alkaline earth salt is magnesium, calcium or barium to reinforcing oil well of the present invention with metakaolin-slag base geological polymer; Further technical scheme is that described alkaline earth salt is magnesium chloride, calcium chloride, bariumchloride, nitrocalcite or nitrate of baryta again.
With in the high temperature retarder, its further technical scheme also can be that described inanimate matter vitriol is zinc sulfate, calcium sulfate, potassium aluminium sulfate or aluminium sodium sulfate to reinforcing oil well of the present invention with metakaolin-slag base geological polymer.
The present invention uses the reinforcing oil well metakaolin-slag base geological polymer of above-mentioned arbitrary high temperature retarder preparation, is made up of following raw materials by weight percent:
Metakaolin 50%～90%;
Blast-furnace slag 10%～50%;
Account for the high temperature retarder of metakaolin and blast-furnace slag weight sum 3%～10% in addition in the raw material in addition.
Wherein said high temperature retarder is made up of following raw materials by weight percent:
A, contain a kind of alkaline earth salt 80%～90% at least;
B, contain a kind of inanimate matter vitriol 10%～20% at least.
The reinforcing oil well of the present invention high temperature retarder of metakaolin-slag base geological polymer, the alkaline-earth metal described in its described alkaline earth salt is preferably magnesium, calcium or barium; Described alkaline earth salt is preferably magnesium chloride, calcium chloride, bariumchloride, nitrocalcite or nitrate of baryta; Described inanimate matter vitriol is preferably zinc sulfate, calcium sulfate, potassium aluminium sulfate or aluminium sodium sulfate.
In the metakaolin-slag base geological polymer of the present invention, its described metakaolin order number is preferably 80～500, and described blast-furnace slag order number is preferably 80～500.
The present invention compared with prior art has following beneficial effect:
(1) high temperature retarder of the present invention can effectively be controlled the rate of setting of reinforcing oil well with metakaolin-slag base geological polymer under high-alkali condition, and can reach more than 5 hours its time of coagulation under 80 ℃ of high temperature, helps the carrying out of engineering construction.
(2) high temperature retarder preparation technology of the present invention is simple, and raw material is easy to get, and cost is lower.
(3) high temperature retarder of the present invention not only has no side effect to the ultimate compression strength of reinforcing oil well with metakaolin-slag base geological polymer, and certain enhancement is arranged.
(4) reinforcing oil well of the present invention mainly is also to have utilized the slag the like waste with metakaolin-slag base geological polymer, can turn waste into wealth, and has enlarged the slag use range simultaneously, promotes scoriaceous efficient utilization, thereby effectively protects environment, reduces environmental pollution.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment.
Embodiment 1
The raw material weight proportioning is:
Metakaolin 800g (300 order), blast-furnace slag (south of the River grinding company limited, 200 orders) 200g, high temperature retarder 60g, wherein 80 parts of bariumchlorides, 20 parts in zinc sulfate in the retardant, the metakaolin-slag base geological polymer of preparation its performance after testing sees Table 1.
Embodiment 2
The raw material weight proportioning is:
Metakaolin 700g (80 order), blast-furnace slag (south of the River grinding company limited, 500 orders) 300g, high temperature retarder 30g, wherein 90 parts of nitrate of baryta, 10 parts of potassium aluminium sulfates in the retardant, the metakaolin-slag base geological polymer of preparation its performance after testing sees Table 1.
Embodiment 3
The raw material weight proportioning is:
Metakaolin 600g (500 order), blast-furnace slag (south of the River grinding company limited, 80 orders) 400g, high temperature retarder 60g, wherein 40 parts of bariumchlorides, 35 parts of nitrate of baryta, 10 parts in magnesium chloride, 15 parts of aluminium sodium sulfates in the retardant, the metakaolin-slag base geological polymer of preparation its performance after testing sees Table 1.
Embodiment 4
The raw material weight proportioning is:
Metakaolin 500g (300 order), blast-furnace slag 500g (south of the River grinding company limited, 300 orders), high temperature retarder 100g, wherein 50 parts of bariumchlorides, 20 parts in calcium chloride, 15 parts in magnesium chloride, 10 parts in calcium sulfate, 5 parts of potassium aluminium sulfates in the retardant, the metakaolin-slag base geological polymer of preparation its performance after testing sees Table 1.
Embodiment 5
The raw material weight proportioning is:
Metakaolin 500g (200 order), blast-furnace slag 500g (south of the River grinding company limited, 200 orders), high temperature retarder 50g, wherein 40 parts of bariumchlorides, 20 parts of nitrate of baryta, 10 parts in calcium chloride, 15 parts in nitrocalcite, 10 parts in zinc sulfate, 5 parts of potassium aluminium sulfates in the retardant, the metakaolin-slag base geological polymer of preparation its performance after testing sees Table 1.
Table 1: metakaolin-slag base geological polymer performance table look-up
As can be seen from Table 1, behind the adding retardant, prolong the time of coagulation of geopolymer significantly, and its degree of mobilization is better, is 24.8cm in metakaolin-slag base geological polymer, and 80 ℃, under the 21MPa condition, the thickening time is 1h32min.Through testing when curing temperature is low (20 ℃), its presetting period of the metakaolin-slag base geological polymer that embodiment 1-5 makes, all more than 48 hours, retarding effect was obvious simultaneously.
Claims (3)
1. reinforcing oil well is characterized in that being made up of following raw materials by weight percent with metakaolin-slag base geological polymer high temperature retarder:
A, alkaline earth salt 80%～90%;
B, inanimate matter vitriol 10%～20%;
Wherein said alkaline earth salt is a kind of or its combination in magnesium chloride, calcium chloride, bariumchloride, nitrocalcite, the nitrate of baryta;
Described inanimate matter vitriol is a kind of or its combination in zinc sulfate, calcium sulfate, potassium aluminium sulfate, the aluminium sodium sulfate.
2. a reinforcing oil well that uses high temperature retarder preparation as claimed in claim 1 is characterized in that being made up of following raw materials by weight percent with metakaolin-slag base geological polymer:
Metakaolin 50%～90%;
Blast-furnace slag 10%～50%;
Account for the high temperature retarder of metakaolin and blast-furnace slag weight sum 3%～10% in addition in the raw material in addition;
Wherein said high temperature retarder is made up of following raw materials by weight percent:
A, alkaline earth salt 80%～90%;
B, inanimate matter vitriol 10%～20%;
Wherein said alkaline earth salt is a kind of or its combination in magnesium chloride, calcium chloride, bariumchloride, nitrocalcite, the nitrate of baryta;
Described inanimate matter vitriol is a kind of or its combination in zinc sulfate, calcium sulfate, potassium aluminium sulfate, the aluminium sodium sulfate.
3. metakaolin-slag base geological polymer according to claim 1 is characterized in that described metakaolin order number is 80～500 orders, and the order number of described blast-furnace slag is 80～500 orders.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100208593A CN101323778B (en) | 2008-07-29 | 2008-07-29 | Metakaolin-slag-based geopolymer for oil field well cementation and high-temperature retarder thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100208593A CN101323778B (en) | 2008-07-29 | 2008-07-29 | Metakaolin-slag-based geopolymer for oil field well cementation and high-temperature retarder thereof |
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| Publication Number | Publication Date |
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| CN101323778A CN101323778A (en) | 2008-12-17 |
| CN101323778B true CN101323778B (en) | 2010-12-29 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153996B (en) * | 2011-02-28 | 2013-02-27 | 金湖凯瑞特石油工程材料有限公司 | Metakaolin-based geopolymer for oil-gas reservoir well cementation and swelling agent thereof |
| CN104312558B (en) * | 2014-11-13 | 2017-03-08 | 中国海洋石油总公司 | Metakaolin waterborne suspension and its preparation method and application and reinforcing oil well cement mortar |
| CN105778875A (en) * | 2014-12-26 | 2016-07-20 | 嘉华特种水泥股份有限公司 | Geopolymer oil well cement |
| AU2018383125A1 (en) * | 2017-12-15 | 2020-06-18 | The Catholic University Of America | Control of time of setting of geopolymer compositions containing High-Ca reactive aluminosilicate materials |
| CN110092597B (en) * | 2019-05-21 | 2020-11-20 | 中国地质大学（北京） | Geopolymer material, adaptive retarder and high-temperature-resistant well cementing cement slurry prepared from same |
| CN110357462A (en) * | 2019-07-29 | 2019-10-22 | 南京工业大学 | Slag-based dry powder geopolymer and preparation method and application thereof |
| CN111517688B (en) * | 2020-04-21 | 2021-11-09 | 杭州砺品科技有限公司 | Concrete retarder and preparation method thereof |
| CN115872645A (en) * | 2021-08-18 | 2023-03-31 | 中国石油化工股份有限公司 | Gradient-cured geopolymer and preparation method and application thereof |
| CN115784663A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Active component slow-release material and preparation method and application thereof |
Citations (4)
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| WO2003078349A1 (en) * | 2002-03-20 | 2003-09-25 | Universität Für Chemie Und Technologie, Prag | Geopolymer binder based on fly ash |
| CN1882516A (en) * | 2003-11-19 | 2006-12-20 | 洛可拉有限公司 | Geopolymer concrete and method of preparation and casting |
| CN101054513A (en) * | 2007-05-21 | 2007-10-17 | 中国石油大学(华东) | Deep water low temperature cementing cement system |
| WO2008017414A1 (en) * | 2006-08-07 | 2008-02-14 | Services Petroliers Schlumberger | Pumpable geopolymer formulation for oilfield application |
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2008
- 2008-07-29 CN CN2008100208593A patent/CN101323778B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003078349A1 (en) * | 2002-03-20 | 2003-09-25 | Universität Für Chemie Und Technologie, Prag | Geopolymer binder based on fly ash |
| CN1882516A (en) * | 2003-11-19 | 2006-12-20 | 洛可拉有限公司 | Geopolymer concrete and method of preparation and casting |
| WO2008017414A1 (en) * | 2006-08-07 | 2008-02-14 | Services Petroliers Schlumberger | Pumpable geopolymer formulation for oilfield application |
| CN101054513A (en) * | 2007-05-21 | 2007-10-17 | 中国石油大学(华东) | Deep water low temperature cementing cement system |
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